Rigidifying composition



Patented Oct. 25, 1932 UNITED STATES PATENT OFFICE BORIS N. LOUGOVOY, OF MONTCLAIR, NEW JERSEY, ASSIGNOR -TO ELLIS-FOSTER COM- PANY, OF MONTGLAIR, NEW JERSEY, A. CORPORATION OF NEW JERSEY RIGIDIFYING COMPOSITION 'No Drawing.

This invention relates to a binding agent or mucilage adapted for various purposes where an adhesive or stifiening agent is required, and relates particularly to solutlons of proteids of a type which are soluble in volatile organic solvents such as the lower alcohols, methyl, ethyl, isopropyl alcohol, and the like.

As types of proteids suitable for the purpose I shall set forth illustratively the employment of gliadin and zein, but it is to be understood that various other proteids orproteins, or like substances, which are soluble in volatile organic solvents, or in mixtures of water-miscible organic solvents and water may be employed.

My composition has a number of uses; for example, it may be employed as a stiffening agent for cloth, or other fibrous materials,

or it may be used asa stifiening agent to hold human hair in place on the head. Also, it may be used as an adhesive for wood, paper and other materials.

The object of the invention is to secure a 55 solution of the glue-like substance in a volatile organic solvent such as alcohol, in order to obtain a quicker drying effect than is possible when water alone is the solvent. Also, it is the object of this invention to employ proteids which are insoluble in water or only partially soluble therein to obtain a higher degree of water resistance than would be secured when starch, glue and similar substances soluble in water, but not soluble in alcohol arezemployed.

In many cases a desirable result is secured by employing a mixed solvent of alcohol and water, the proportion of one solvent to the other varying under conditions of use, but

preferably using not less than to per cent of water or of alcohol in the mixture.

Such a Water-alcohol vehicle is desirable in the treatment of human hair to hold it in place, because the water present softens the hair so that it may be combed or brushed into place, or by means of waving devices, and

the like, allowed to'dry and set in undulan tions. Hitherto the compositions used for the purpose have been the usual water-solu- Application filed January 18, 1928. Serial No. 247,759.

ble mucilages which dry slowly and are there-- fore undesirable.

, In my composition a sufiicient proportion of ethyl alcohol, isopropyl alcohol, and the like, may be present to obtain a quick-drying clfect. F nrthermore, the presence of such a significant proportion of alcohol is of value in preventing the catching of colds by wetting the head and then being exposed to cold Weather or draughts. The alcohol in the vehicle has the property of acting on the pores of the scalp in such a way that resistance to catching of colds is created. Hence the composition may be applied freely in the wintertime and a person may venture into the open air even though the hair is still Wet with the composition without the customary apprehension of catching cold such as arises when the hair and scalp is wet with water alone.

There follow various formulae which show how my invention may be embodied in an illustrative way.

When a preparation such as a waving fluid or hair dressing is made it should embody various other requirements besides the re quirement of a specific binding action.

Such a preparation should not contain any harmful agent, or any agent with an oftensive odor, or a material which does not appeal to the general-taste owing to its color etc. All ingredients should be of such a nature as to be easily washable out from the hair with soap and water.

The binder itself should be of such a nature as to produce only a specific action; it should keep the hair in place and at the same time it should not stick it together too much, or produce any ditiiculty in combing the hair after application of such preparation. After being applied on and dried, such a binding agent should produce a certain amount of gloss. It should not flake out after the hair has been waved, and it should possess a certain degree of durability, i.- e., it should keep the produced eilect for a certain length of time, which in some cases such as artificial waves should be a period of several days.

When a preparation intended for use in producing artificial waves on the hair is made there are additional requirements to fulfil in connection with the ease of operating such a preparation. For example, the preparation when used for waving is done by fin er, and it should therefore be easily handled y o rator, which means that it should not she to the finger of operator, thus handicapping his operations, and it should possess a certain amount of body, in'other words it should not to be fluid, so that it would run out between the fingers. The latter requirement at the present time, when aqueous preparations of that kind are used, is accomplished by employing a binder such as a flax seed, a substance which swells in water and which forms a celloid in the form 0 'a suspended g l.

While there are a number of substances both inorganic and organic which form such colloidal suspension in aqueous solution, and while there also could be found a number of substances which form a gel in a strong alcohol, as for instance, derivatives of cellulose, sugar and some metallo-organic com pounds, the difiiculty immediately arises when a mixture of an alcohol and water is considered as acolloidizingmedium. Inmost cases when a substance forms a colloidal gel in water as a medium, the collodial state is destroyed by addition of alcohol, and vice versa when a substance such as, for example, cellulose ester forms a colloidal solution in alcohol, this is destroyed by addition of water. As stated at the beginning, in a reparation such as a waving uid or a hair ressing, it is necessary to have a certain, and sometimes a substantial, amount of water present in order to secure a proper moistening of the hair for combing purposes, and for the convenience of the operator producing such artificial waves.

It was therefore necessary to find asubstance which is soluble not only in water and alcohol, but which forms a suspended colloid in this medium, and at the same time which satisfies .those other requirements heretofore stated such as being physiologically harmless, washable with soap and water, and easily procurable on an open market at a reasonable price.

In the course of this investigation it was found that certain cereal proteids such as gliadin and zein might serve the urpose under certain definite conditions. liadin, which is a wheat proteid, when used in a pure state, is insoluble both in cold water and in strong alcohol, but I have found that it dissolves in a mixture of those two solvents, or rather in a diluted alcohol. My researches have shown that a proper and true collodial solution is obtained only with a definite ratio of alcohol and water, and that this ratio is quite limited. The ratio of alcohol to water which produces a clear collodial solution of gliadin approximates that of the mixture of spondi ri gi to the alcoholic strength'of 70 per cent. e addition of even a few cubic centimeters of either alcohol or water to 100 cubic centimeters of the above mixture immediately produces some coa lation of the proteids, which results in a c oudy solution; As in all cases of colliodial phenomena, the

viscosity or density of such a colloidal solution varies, depending upon how said solution is made; for instance, a hi her viscosity (heavier body) is obtained w en gliadin is dissolved or extracted from wheat directly with 70 per cent alcohol, than when this' gliadin is first dissolved in a different mixture of water and alcohol, and the turbid solution thus obtained then clarified by addition of either water or strong alcohol. A similar phenomenon was observed with zein, which is a proteid from corn. There is very little information about this substance in the literature. This roteid is described as soluble in strong alco 01 with the formation of a colloidal solution. Experiments along this line reveal that this is true only if the substance is in a highly urified state, which would be impractical or commercial use. However, as in the case of gliadin, it was found that zien prepared as described later could be put into colloidal solution when a certain mixture of water and alcohol is used. A suitable mixture for zein was found to be in the neighbourhood of 92 parts of 95 per cent ethyl alcohol and 8 parts of water, corresponding to a strength of ethyl alcohol of about 88-90 er cent.

In order to ilustrate how a proteid of a suitable type for the present invention could be prepared in the simplest possible way, a preparation of gliadin and zein which were used in various formulae given below will be now described:

Preparation of gliadin As the source of gliadin a number of cereals can be used, among which are wheat, oats, rye or barley. The best material, however, is wheat flour, which is rich in gluten.

It is known that the amount of gluten in a wheat flour varies according to the climate, soil, kind of fertilizer used, etc. (In the present work gluten flour which contains about per cent of gluten, was principally used.) To prepare gliadin in a substantially pure state the following method was used:

Wheat flour was made into a dough with warm water. The dough was then placed in a canvas bag and washed with running water until the wash water was perfectly clear. The gluten so obtained was pressed to squeeze out an excess of water, and was then placed into a flask with double its volume of r cent ethyl alcohol, and boiled under a refliix condenser for two hours. The clear alcoholic extract was cooled, allowed to stand for a few hours, decanted from a small sediment which resulted upon cooling, and then evaporated to one-half of its volume, cooled again and filtered from sediment through a closely Woven cloth. The clear alcoholic solution of gliadin so obtained was finally evaporated to dryness and the gliadin was obtained in the form of a glue or gelatin-like flakes. The

liadin thus obtained was insoluble in strong %95 per cent) ethyl alcohol, as well as in even hot water, but it was easily soluble in ethyl alcohol of about 70 per cent strength. It was somewhat less soluble in isopropyl alcohol, requiring in this case at least 30 volumes of water to 80 volumes of alcohol in order to obtain a clear solution on cooling.

As stated before, for practical purposes it is not necessary, however, to go throu h so many operations in order to obtain ghadin in the pure state, and good results were obtained in a more simple manner for the preparation of this material according to the following procedure.

500 grams of gluten flour containing about 50% gluten was digested with a hot mixture of 700 cubic centimeters of ethyl alcohol and 300 cubic centimeters of water under reflux.

The material became very pasty, and was difiicult to filter. It was filtered by means of a muslin bag, and about 400 grams of very viscous, turbid, slightly yellow solution was collected. This solution contained about 11 per cent of solid material which after being applied onto a glass and dried formed a water-white transparent and somewhat brittle film.

It was found that this crude extract could be used directly in the preparation of a waiving fluid or a hair dressing, in place of a solution made by dissolving isolated gliadin in 70 per cent alcohol.

Preparation of zez'n Pure zein was prepared in the following manner:

965 grams of a cornmeal was refluxed with 600 grams of ethyl alcohol, 95 per cent strength, and was then allowed to stand for several hours. The solution was warmed again and then filtered hot. The filtrate was evaporated to one-half its volume and then poured into a large amount of cold water. The precipitate which formed was filtered through a muslin bag, carefully washed with water, the residue then dried in an oven at degrees centigrade, and oil then extracted from it with ether. The ether extract was of a deep yellow color, while the residue from the extract after being washed with a fresh portion of ether was an almost while gelatinlike material. This material was again refluxed with twice the amount of a strong ethyl alcohol, and the whole treatment repeated. Finally about 3 grams of a waterwhite gelatin-like substance was obtained, which could be considered as a substantially pure Zein. This material was soluble in 95 per cent ethyl alcohol.

As in the case of gliadin, it would not be practicable to use such an elaborate purification, and a more simple method could be employed which consists in the refluxing of cornmeal with about twice its volume of strong alcohol, with subsequent filtration and evaporation of the extract. If a material of greater purity is desired, the first alcoholic extract may be poured into a large volume of water (dispensing with the concentration procedure) and the precipitate so obtained can be used for the preparations described in the following examples.

Waving fluid A toilet preparation which is known commercially as a waving fluid is a preparation designed for use in the so-called cold method of producing artificial hair waves. According to this method the operator performing the work first moistens the hair to be waved with such. a preparation and then works out the waves with his fingers. Finally the waved hair is tediously dried, a procedure which usually requires a half hour or more under treatment with a current of heated air supplied by a blower. There are therefore numerous requirements which must be fulfilled in order to obtain a satisfactory product. In the first instance such a preparation should leave after drying a suflicient amount of binder on the hair to preserve the waves. Considering that during the process of waving only'a part of the hair can be worked on at a time, it is important that the finished part which is still wet does not change its shape under the action of the additional weight due to moistening of the hair. Consequently the waving preparation should be such as to form a substantially strong binder, even when the hair is not dry. On the other hand the relative amount of a solid binder in a waving fluid should not be too great, as otherwise it will produce a sticking or gluing effect on the hair after it is dry, and will make the hair diflicult to comb. To accomplish this it would be necessary to have a substance which, after being dissolved in a solvent, even in a small amount, swlls and forms a heavier body, or in other words which is capable of forming, even with a small amount, a solution of increased viscosity.

Another consideration requires the absence of stickiness during the waving treatment. A suitable liquid should not form a sticky residue when a portion of the solvent is evaporated during the waving operation. This is particularly important when a wav- Ill! ing preparation contains alcohol as a solvent, as in such case evaporation will be faster, as compared with the usual preparations in use at the present time, having water as a solvent. If a sticky residue is forming durin the wavin o eration it will tend to stick t e hair to t e ngers of the o rator, thus destroying the already arrange waves and evidently handicapping and annoying the operator performing the treatment.

This inconvenience was immediately discovered when a simple solution of gliadin in 70 per cent alcohol was tried out as a hair waving preparation. Illustration of such solution is given in Example I.

Example I 50 parts of 10 per cent extract oi gluten flour with 7 per cent alcohol. 50 parts of 7 0 per cent ethyl alcohol. 0.5 parts of glycerol.

It was therefore necessary to devise a formula which would eliminate this disadvantage. After a number of unsuccessful.

tests it was found that the addition of a certain amount of an alcoholic extract of flax was obtained with castor oil and its modifications, such as Turkey red oil. Although stickiness was eliminated by the addition of flax seed extract, a further improvement became necessary since this addition produced a certain lowering of viscosity, probably due to the action of some oil globules, thus requiging the introduction of a protective colloi A saturated aqueous solution of soluble egg albumen was found suitable for the purpose, and a formula for a waving fluid which was found satisfactory is given in Example II.

Ewample I I 66 parts by volume.

2 drops of glycerine was added to each 100 cubic centimeters of the above mixture as a softening agent.

Perfumes.

The alcoholic extract of flax seed used in this formula was made by refluxing a ground flax seed with twice its amount of 95 r cent ethyl alcohol for 2 hours, and filterlng said solution.

The waving fluid made according to this formula was actuall tested for the purpose by a roiessional hairdresser and was found satis actory. It was convenient to operate, and after being dried out produced good durable waves.

In order to give a more exact proportion of ingredients for a composition of the kind given in Example II, the above formula was modified as follows:

Example III 100 parts by volume of 5 per cent solution of gliadin in 7 0 er cent ethyl alcohol. 50 parts by volume 0? 10 per cent alcoholic flax seed extract. parts by volume of 95 per cent ethyl al- 001101. parts by volume of water.

200 parts by volume.

To each 200 cubic centimeters of the above solution the following was added:

1 gram of soluble egg albumen. 2 grams of glycerol.

Perfumes as desired.

The egg albumen is dissolved in water, then added to the mixture of other ingredients.

This composition had a somewhat heavier body and was noticeably more slippery to the touch when the hair waves were worked out with the fingers.

Ewample IV For the purpose of obtaining a higher gloss and an increased pliability, it may be desirable in certain cases to incorporate lanoline gslan ingredient of the waving fluid, as given e ow:

100 parts by volume of 5 per cent solution of gliadin in 7 0 per cent ethyl alcohol. parts by volume 0 10 per cent alcoholic flax seed extract. 20 parts by volume isopropyl alcohol of 98 per cent. 30 parts by volume water.

To each 200 grams of the above mixture the following is added:

1 gram of soluble egg albumen. 1 gram of glycerine. 1 gram anhydrous lanoline.

In preparation of this solution lanoline is Y illustrated in Example V.

Ewample V 100 grams of 5 per cent solution of zein. 25 grams of alcoholic extract of flax seed. 1.5 grams glycerine.

Gelatin was also found useful for the purpose under certain conditions, either as a partial substitute for gliadin or as a protective colloid. Although gelatin is known to be insoluble in a relatively strong alcohol, it was'found that in the presence of a small amount of some organic acids a colloidal solution of gelatin in 70 per cent alcohol could be produced. Acetic acid is the most eflicient acid for the purpose, but is not so desirable for use in a toilet preparation. 7 It was observed that malic, citric, or tartaric acid produce a similar effect, the tartaric acid being the most eiiicient of the above three acids. Lemon juice was found to be the most practical for the purpose, because this material is known to be not only harmless for the hair, but is claimed to be even beneficial, and has been recommended for use as an ingredient in water for Washing the hair. In addition to being an agent capable of stabilizing gelatin solutions, lemon juice or a small amount of the above mentioned organic acids have a beneficial eflect upon the solution of gliadin since they tend to increase the body or viscosity of the gliadin solution.

An illustration of the preparation embodying this kind of material is given in Examples VI and VII.

Example VI 2 grams of glycerol.

Example 7]] 50 parts by weight of 5 per cent gliadin solution in 7 0 per cent alcohol.

50 parts by weight of 5 per cent gelatin solution in 50 per cent alcohol containing lemon juice.

10 parts by weight 10 per cent alcoholic flax seed extract. I

20 parts by weight isopropyl alcohol.

20 parts by weight of water.

20 grams glycerin.

When comparing the foregoing hair dressing compositions with those now in general use the following advantages may be mentioned.

The greater number of hair waving compositions in present use represent a colloidal solution of such substances as flax seed or gum tragacanth in water. Such aqueous solutions, after being applied for waving treatment, require a rather lengthy drying operation, usually performed by applying a stream of warm air. When a water-alcohol mixture is used such drying operation is considerably shortened and the temperature of the warm air may also be greatly reduced, thus minimizing the danger of catching cold, especially in cold weather.

Another and possibly more important advantage of waving compositions of the present invention is found in greater durability of finished waves, owing to the greater water resistance of the binder used in their preparation. Both flax seed and gum tragacanth, being water soluble substances are easily affected by moisture of the air, which results in a fact known to everybody, namely that artificial waves are easily destroyed on a rainy day or on a humid summer evening, or when used at the seashore. Both gliadin and zein are substances insoluble in cold water, and therefore are not hydroscopic. Consequently they furnish abetter guarantee towards greater durability of artificial waves and often eliminate the troublesome precautions usually employed by a person on leaving a hairdresser on a rainy day in order to preserve the good appearance of the waved hair.

H air dressing Hair dressing compositions designed for keeping the hair in place after it is combed, in all their essential requirements are similar to the foregoing waving fluids. However, some specific conditions should be considered in such preparations, as for example a somewhat greater wetting action on the hair, permitting easy combing. As stated elsewhere, when water alone is used there always exists the danger of catching cold bywetting the head and then having it exposed to cold weather or draught. No such danger would exist when an alcohol-water mixture is used. A hair dressing should hold the hair firmly in place and give a neat appearance and certain degree of gloss to the hair. It may also be of advantage to incorporate into a hair dressing composition some kind of a hair tonic.

An illustration of such a preparation is given in Example VIII.

Example VIII 25 parts by weight isopropyl alcohol 98 per cent.

'50 parts by weight water.

3 parts by weight gliadin.

0.25 parts by weight quinine sulphate.

1 drop of glycerine to each 100 cubic centimeters of solution.

Perfumes if desired.

Proteids as a starch substitute Proteids of the type discussed in the present specification are also found useful in certain cases as a substitute for starch for stiffening cloth, as illustrated below.

Example IX 5 per cent solution of zein in 90 per cent ethyl alcohol could be used for such a purose.

When a light muslin cloth is soaked in such a solution and then dried and ironed a stiiiening effect like that of starch is produced. The zein which forms a flexible gelatin-like film under those conditions will not only stiffen the cloth without destroying its liability, but the cloth will recover its s a e after being wrinkled, a property which won d be of practical value especially when the solution is used to stiffen ladies summer dresses. The use of proteids of gliadin and zein tip: for such a purpose, in addition to the a ve, will have another practical value owing to their resistance towards humiditx of the air, as in the case of a waving flui These materials when used for stiffening cloth in place of a starch produce an article which is more durable towards weather conditions, thus assuring a better rotection against moisture, and preserving a tter ap- P68181100. g

A binding agent for paper when making such articles as paper utensils for food, as, for example, paper spoons, forks or plates, it is evidently necessary to use such materials as will not raise any doubt about their being injurious for the health. The use of a. material which in itself is a food ingredient, such as a cereal proteid, will therefore have a decided advantage pggvided it accomplishes its purpose. In ma g paper utensils, particularly such articles as spoons or forks, the paper used should satis- 'y the required conditions as to strength and toughness. A paper spoon should be strong and rigid enough to withstand without breaking such tension as, for example, is produced when a hard ice cream is cut, and it should be sufliciently tough so as not to break into pieces if the tension applied should exceed a safe limit. In such a case the spoon should only bend at a certain point, thus permitting the person to finish his dish. I

To accomplish this a laminated paper made of several sheets of thin aper joined together by means of a suite 1e adhesive may be used. A flexible non-brittle binder for paper is desirable for such a urpose. Since any deep impregnation of a brous material usually tends to increase the brittleness of the film it is desirable to employ a substance which does not penetrate dee 1y into the fibres, but forms mainly an adhesive layer on the surface of the paper, thus preserving the natural flexibility of the paper. If desirable a certain amount of softening agent may be added to such an adhesive.

It is also desirable that those adhesive layers usedin making the laminated paper possess a certain degree of resistance towards atmosfpheric moisture, because if such adhesive is a ected with moisture there will be danger of softening, i. e., loss of ri idity if pa er articles such as spoons are eft exposed to a humid air for a lon time. An illustration of how cereal protei s may be used for such a purpose is given in Example X.

Example X Three sheets of a jute paper of about 0.5 mm thickness were impregnated with a 10 per cent solution of gliadin in per cent alcehol containing about per cent of glycero The paper was then partially dried at room tem rature by means of a draught of air, unti a sticky surface was obtained, and then all three sheets were pressed to ther and finally dried in an oven at 60 to 0 C. for a few minutes. A stifi board was produced in this manner. This board was then superficially moistened with water, so as to make it slightly flexible, and paper spoons were starenped from it, which were afterwards dri in an oven at 67 C. for 30 minutes.

A sizing material An illustration of how cereal proteids my be used as a sizing for paper is 'ven 111 Example XI. g1

proteids having similar characteristiw and properties for the purposes in hand.

What I claim is:

1. As a hair dressing medium an aqueous alcohol-soluble proteid in a solution comprising a substantial proportion of a volatile alcohol. I

2. As a hair dressing medium an aqueous alcohol-soluble proteid in a solution comprising water and a substantial proportion of a volatile alcohol miscible therewith.

3. As a hair dressing composition, a solution of gliadin in alcohol and water.

4. As a hair dressing composition, a solution comprising a proteid of the gliadin-zein group, alcohol and water.

BORIS N. LOUGOVOY. 

